The present invention relates to a porous thermoplastic resin film suitable for use as a separator of a cell, and more particularly to a porous thermoplastic resin film suitably used as a separator of an electrolytic capacitor, a lithium cell, a fuel cell, a battery, or the like.
Hitherto, as a porous thermoplastic resin film having air permeability, there is known, for example, a porous film obtained by stretching a thermoplastic resin film containing a filler. Such a porous film having air permeability has a good moisture permeability or airy property, and is used widely as a hygienic material such as a disposable diaper.
For example, Japanese Unexamined Patent Publication No. 09-176352 discloses a porous film obtained from a polypropylene composition composed of 100 parts by weight of polypropylene, 10 to 120 parts by weight of resin particles having an average particle diameter of 0.01 to 10 xcexcm, and 0.01 to 3 parts by weight of a xcex2-crystal type nucleating agent. The porous film disclosed above has a gurley value, which shows air permeability, of 10 to 30000 sec/100 cc, a porosity of 10 to 70%, and the maximum pore diameter of 0.1 to 9 xcexcm. However, according to the studies made by the inventors of the present invention, the above porous film, when used as a separator in a cell, particularly a lithium cell, increases the internal resistance of the cell and is not sufficient as the separator.
An object of the present invention is to provide a porous thermoplastic resin film suitable for a separator of a cell.
The inventors of the present invention have made eager studies in order to develop a porous thermoplastic resin film that gives a low internal resistance when the film is used as a cell separator, and have found that a porous film comprises a thermoplastic resin and a filler and satisfies a particular relationship among the thickness, the gurley value, and the average pore diameter thereof functions well when used as a cell separator. Thus, the present invention has been completed.
The present invention provides a porous film comprising a thermoplastic resin and a filler, wherein XR defined by the following formula:
XR=25xc3x97TGURxc3x97d2/Y
is smaller than 5, where Y (xcexcm), TGUR (sec/100 cc), and d (xcexcm) represent the thickness, the gurley value, and the average pore diameter of the film, respectively.
Further, the present invention provides a separator for a cell which separator is made of the said porous film, and a cell having the said separator.
According to the studies made by the inventors of the present invention, the porous polypropylene film disclosed in Japanese Unexamined Patent Publication No. 09-176352, for example, has the parameter XR as defined above of about 10 to 800; and the porous film increases the internal resistance of the cell when used as a separator of a cell. Thus the cell obtained from above porous film does not provide a sufficient performance. In contrast, the porous film provided by the present invention has a value XR of less than 5 and reduces the internal resistance of the cell, when the porous film provided by the present invention is used as a separator of a cell. Thus the cell containing the porous film of the present invention shows a high performance as a cell.
In the porous film of the present invention, the value XR defined by the following formula:
XR=25xc3x97TGURxc3x97d2/Y
is less than 5, preferably not more than 3, more preferably not more than 2, where Y (xcexcm), TGUR (sec/100 cc), and d (xcexcm) represent the thickness, the gurley value, and the average pore diameter of the porous film, respectively. A porous film having a value XR of 5 or more, when used as a separator, increases the internal resistance of the cell, and does not provide a cell functioning well.
The gurley value is represented by the period of time that is needed for a predetermined amount of air (typically 100 cc) to permeate through a predetermined area (typically 645.16 mm2) of the film, and is measured according to JIS (Japanese Industrial Standard) P8117, as will be described later.
The average pore diameter d is typically measured by the bubble point method. The bubble point method is the method which includes a step of filling micro pores of a film with liquid and a step of squeezing the liquid from the micro pores by the force prevailing the surface tension of the liquid filling the micro pores. The average pore diameter d can be obtained according to ASTM F316-86 as will be described later.
Here, the gurley value TGUR and the average pore diameter d of the porous film of the present invention are not particularly limited as long as they are combined to give a parameter XR of smaller than 5; however, the gurley value TGUR is preferably within the range from 40 to 3000 sec/100 cc, more preferably within the range from 60 to 1000 sec/100 cc, and the average pore diameter d is preferably within the range from 0.04 to 0.4 xcexcm, more preferably within the range from 0.04 to 0.2 xcexcm.
The film thickness Y of the porous film of the present invention is typically from 1 to 200 xcexcm, preferably from 5 to 50 xcexcm, more preferably from 5 to 30 xcexcm.
A combination giving a value XR of less than 5 may be obtained in the following manner. Typically, a predetermined film thickness Y xcexcm is first set, and then the value TGURxc3x97d2 is determined in accordance with the value of Y so that the value XR will be less than 5. Since TGUR is generally correlated to the pore diameter d and the number of pores, it is sufficient to determine the relationship between d and TGUR experimentally. Since the pore diameter and the number of pores are correlated to the average particle size and the filling amount of the filler as described later, respectively, it is sufficient to set the particle size and the filling amount of the filler so that the value XR will be less than 5. Alternatively, for example, TGURxc3x97d2 may be determined in advance by experimental measurement or the like, and the value of Y may then be set so that the value XR will be smaller than 5.
The thermoplastic resin used in the porous film of the present invention may be, for example, a polyolefin resin such as a homopolymer of olefin such as ethylene, propylene, butene, or hexene, or a copolymer of two or more kinds of these olefins, or a copolymer of one or more kinds of these olefins and one or more kinds of monomers polymerizable with the olefins; an acrylic resin such as polymethyl acrylate, polymethyl methacrylate, or ethylene-ethyl acrylate copolymer; a styrenic resin such as butadiene-styrene copolymer, acrylonitrile-styrene copolymer, polystyrene, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, or styrene-acrylic acid copolymer; a vinyl chloride resin; a vinyl fluoride resin such as polyvinyl fluoride or polyvinylidene fluoride; an amide resin such as 6-nylon, 6,6-nylon, or 12-nylon; a saturated ester resin such as polyethylene terephthalate or polybutylene terephthalate; polycarbonate; polyphenylene oxide; polyacetal; polyphenylene sulfide; a silicone resin; a thermoplastic urethane resin; polyetheretherketone; polyether imide; thermoplastic elastomers of various kinds; cross-linked products of these; or the like.
The porous film of the present invention may contain one or more kinds of thermoplastic resins.
Among the aforesaid thermoplastic resins, a porous film made of a polyolefinic resin is excellent in solvent resistance, and is melted to close pores thereby at a temperature law enough to restrain the abnormal reaction of the cell. Thus, the porous film made of a polyolefin resin may be preferable for using as a separator for a lithium cell.
The olefins used in the present invention may be, for example, ethylene, propylene, butene, hexene, or the like. Specific examples of polyolefins include polyethylenic resins such as low-density polyethylene, linear polyethylene (ethylene-xcex1-olefin copolymer), and high-density polyethylene, polypropylenic resins such as polypropylene and ethylene-propylene copolymer, poly(4-methylpentene-1), poly(butene-1), and ethylene-vinyl acetate copolymer.
In particular, a porous film made of a polyolefinic resin that contains a polyolefin having a molecular chain length of 2850 nm or more has an excellent strength, and can give a cell having a lower internal resistance when used as a separator. The polyolefinic resin preferably contains at least 10 wt %, more preferably at least 20 wt %, still more preferably at least 30 wt %, of polyolefin having a molecular chain length of 2850 nm or more.
The filler to be used in the porous film of the present invention may be either an inorganic filler or an organic filler. Examples of the inorganic fillers include calcium carbonate, magnesium carbonate, barium carbonate, talc, clay, mica, kaolin, silica, hydrotalcite, diatomaceous earth, calcium sulfate, magnesium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, alumina, zinc oxide, zeolite, and glass powder. Particularly, calcium carbonate, hydrotalcite, barium sulfate, magnesium hydroxide, and alumina are preferable.
The organic filler to be used in the present invention may be selected from a variety of resin particles. Among these, homopolymers of styrene, vinyl ketone, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, or methyl acrylate, copolymers of two or more kinds of monomers selected from the above group of monomers, and condensation polymers such as melamine and urea may be mentioned.
The average particle size of the aforesaid filler contained in the porous film of the present invention is preferably not more than about 1 xcexcm, more preferably from about 0.05 to about 1 xcexcm, still more preferably from about 0.1 to about 0.6 xcexcm. Typically, the average particle size of the filler contained in the porous film is approximately equal to the average particle size of the filler before blending.
Further, as will be described later, an unstretched film obtained from a thermoplastic resin filled with filler is stretched to generate voids at the interface between the filler and the resin, and then, to create through-hole. Generally, the average pore diameter of the formed pores is approximately equal to the average particle size of the filler that fills the thermoplastic resin.
Further, a porous film containing a filler having an average particle size of not more than about 1 xcexcm generally has a small average pore diameter d and has a small value of XR.
As a result, the porous film of the present invention can give a cell having a considerably low internal resistance when used as a separator. The average particle size of the filler in the porous film of the present invention is an average of the diameters measured for all the particles found in the field of view having a size of 10 xcexcmxc3x9710 xcexcm when the porous film surface is observed by a scanning electron microscope (SEM).
The content of the filler in the present invention is preferably at most 85 parts by volume, more preferably at most 70 parts by volume, with respect to 100 parts by volume of the thermoplastic resin in view of the stretchability. Generally, since the number of pores in the porous film is proportional to the filling amount of the filler and the gurley value is correlated to the number of pores, the filling amount is preferably at least 15 parts by volume, more preferably at least 25 parts by volume in view of reducing the value of XR to be smaller than 5.
Since the porous film of the present invention contains a filler, the porous film has good slip properties, and hence a series of steps of assembling the cell can be smoothly carried out.
The porous film of the present invention may contain additives such as a stretching aid made of aliphatic ester, low-molecular-weight polyolefin resin, or the like, a stabilizer, an antioxidant, an ultraviolet absorber, a fire retardant, and a nonionic surfactant.
The porous film of the present invention can be produced, for example, in the following manner. First, a thermoplastic resin and a filler as well as optional desired additives such as a nonionic surfactant are mixed with the use of a mixing apparatus such as a roll, a Banbury mixer, a monoaxial extruder, or a biaxial extruder to prepare a resin composition from which a film is produced by a film molding method such as inflation processing, calendering processing, or T-die extrusion processing.
For example, a resin composition made of a thermoplastic resin containing at least 10 wt % of polyolefin having a molecular chain length of 2850 nm or more and a filler can be prepared by blending a polyolefin [A] having a weight average molecular chain length of 2850 nm or more and polyolefin wax [B] having a weight average molecular weight of 700 to 6000 in a weight ratio of [A]/[B]=90/10 to 50/50, further adding a predetermined amount of filler, and kneading the mixture with the use of a kneading apparatus having, in a barrel, a screw constituted by a combination of at least two kinds of segments, i.e. a full flight screw and a kneading block so as to enable strong kneading. Particularly, it is preferable to use a kneading apparatus having a ratio L/D of at least 30, a ratio Lf/D of at least 3, and a ratio Ln/D of at least 5, where L (mm), D(mm), Lf(mm), and Ln(mm) represent the total length of the screw, the inner diameter of the barrel, the combined length of the full flight screws, and the combined length of the kneading blocks, respectively.
Further, it is preferable to use an apparatus having a value xcex1 within the range from 35 to 60, a ratio M/D within the range from 0.15 to 0.25, where xcex1 (xc2x0) and M (mm) represent the flight angle of the full flight screw and the depth of the screw groove of the full flight screw, respectively.
Here, in the present invention, the molecular chain length, the weight average molecular chain length, the molecular weight, and the weight average molecular weight of the polyolefin were measured by GPC (gel permeation chromatography), and the mixing ratio (wt %) of the polyolefins within a specific molecular chain length range or within a specific molecular weight range can be determined by integration of the molecular weight distribution curve obtained by the GPC measurement.
The molecular chain length of the polyolefin is the molecular chain length measured by GPC (gel permeation chromatography) as converted in terms of polystyrene and is, more specifically, a parameter determined according to the following procedure.
Namely, as the moving phase in the GPC measurement, one makes use of a solvent that can dissolve both a sample to be measured its molecular weight and a standard polystyrene having a known molecular weight. First, GPC measurement is carried out on plural kinds of standard polystyrene having different molecular weights to determine the each holding time of plural kinds of standard polystyrene. With the use of a Q factor of polystyrene, the each molecular chain length of standard polystyrene is determined and, from this, the each molecular chain length of standard polystyrene and the holding time corresponding thereto are found out. Here, the molecular weight, the molecular chain length, and the Q factor of standard polystyrene are under the following relationship:
molecular weight=molecular chain lengthxc3x97Q factor.
Next, GPC measurement is carried out on a sample to obtain a holding timexe2x80x94eluted component amount curve. Assuming that the molecular chain length of standard polystyrene having a holding time of T in the GPC measurement of standard polystyrene is L, the xe2x80x9cmolecular chain length as converted in terms of polystyrenexe2x80x9d of a component having a holding time of T in the GPC measurement of a sample is defined as L. With the use of this relationship, the molecular chain length distribution, as converted in terms of polystyrene, of the sample (the relationship between the molecular chain length as converted in terms of polystyrene and the eluted component amount) is determined from the aforesaid holding time eluted component amount curve of the sample.
Next, this film is stretched to form pores at the interface between the filler and the resin. The stretching is carried out in a monoaxial direction or in biaxial directions with the use of a roll stretcher, a tenter stretcher, or the like.
The stretching temperature is preferably lower than or equal to the melting point or the softening point of the thermoplastic resin.
For example, if the thermoplastic resin is a polyolefin resin, the stretching temperature is preferably lower than or equal to the melting point of the polyolefin resin, and particularly the range from 50 to 150xc2x0 C. is preferable. The stretching ratio is preferably about 2 (twofold) to about 10 (tenfold), more preferably about 3 (threefold) to about 8 (eightfold). If the stretching ratio is less than about 2, the pores of the film are less likely to be suitably enlarged and a porous film thus obtained may have a parameter XR more than 5. On the other hand, if the stretching ratio exceeds about 10, the thickness of the film thus obtained may be uneven and liable to be broken during the stretching.
The thermoplastic resin constituting the porous film of the present invention may be cross-linked by radiation of radioactive rays. A porous film made of a cross-linked thermoplastic resin is more excellent in heat resistance and strength than a porous film made of a non-cross-linked thermoplastic resin.
In view of acheiving an excellent ion conductivity when a porous film is used as an ion transmission film, the porous film of the present invention may preferably has a thickness of about 3 to about 50 xcexcm. In this case, the thermoplastic resin constituting the porous film is more preferably cross-linked by radioactive radiation. Generally, when the thickness of a porous film is reduced, there is a problem of decrease in the film strength. In contrast, the porous film of the present invention having a thickness of about 3 to 50 xcexcm and made of a thermoplastic resin that is cross-linked by radiation of radioactive rays can be an ion transmission film being excellent in ion conductivity and having a high strength.
The porous film of the present invention made of a cross-linked thermoplastic resin can be obtained by radiation of radioactive rays on a porous film of the present invention that is produced with the use of a non-cross-linked thermoplastic resin.
The type of radioactive rays to be radiated on the porous film of the present invention for cross-linking is not particularly limited; however, gamma rays, alpha rays, electron beams and others are preferably used, and in particular, electron beams are more preferable in view of production speed and safety.
The radiation source to be used is preferably an electron beam accelerator having an acceleration voltage of 100 to 3000 kV. If the acceleration voltage is lower than 100 kV, the transmission depth of the electron beams may be insufficient, whereas if the acceleration voltage is higher than 3000 kV, the apparatus may be extensive and not preferable in view of costs. Examples of the radioactive ray radiation apparatus include electron beam scanning type apparatus such as a Van de Graaff type and electron-beam-fixed conveyor-moving type apparatus such as an electron curtain type.
The amount of radioactive rays to be absorbed is preferably 0.1 to 100 Mrad, more preferably 0.5 to 50 Mrad. If the amount of absorbed rays is smaller than 0.1 Mrad, the effect of cross-linking the resin may be insufficient, whereas if the amount of absorbed rays is larger than 100 Mrad, the strength is considerably reduced, so that it is not preferable.
Radiating radioactive rays onto the porous film of the present invention may be conducted under air or inert gas such as nitrogen, and preferably under inert gas.
Also, in radiating radioactive rays, the porous film of the present invention may be impregnated with another monomer compound or polymer, and the radioactive rays may be radiated to carry out reaction for cross-linking or graft polymerization. Examples of the compounds with which the porous film of the present invention is mixed or impregnated include styrene, divinyl benzene, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, fluorine compounds, homopolymers and copolymers of these, and sulfonic acid derivatives and phosphoric acid ester derivatives of the above-mentioned monomers or polymers.
The above-mentioned porous film of the present invention can be suitably used as a separator in a cell. Therefore, the separator for a cell according to the present invention is characterized by being made of the aforesaid porous film of the present invention, and the cell of the present invention is characterized by having a separator made of the aforesaid porous film of the present invention. Examples of cells to be used in the present invention include lithium primary cells, lithium secondary cells, nickel-hydrogen cells, and alkali-manganese cells.
For example, if the cell of the present invention is a lithium secondary cell, the negative electrode may be made of lithium metal, an alloy of lithium and aluminum or the like, or a carbon electrode formed to be capable of absorbing and desorbing lithium ions, and the positive electrode may be made of a known electrode such as manganese dioxide. The form of the cell may be as follows. For example, the porous film of the present invention (i.e. the separator) may be rolled up between the positive electrode and the negative electrode, or alternatively each electrode may be wrapped up with a bag made of the porous film of the present invention. The obtained product is then inserted into a case together with an electrolytic solution and sealed to obtain a cell. The electrolytic solution to be used in the present invention may be, for example, a non-aqueous solution obtained by dissolving an electrolyte such as LiPF6 into a non-protonic polar solvent such as ethylene carbonate (EC), ethyl methyl carbonate, or dimethyl carbonate (DMC).